TWI595017B - Active energy ray-curable composition, cured product thereof, and article having a cured coating film thereof - Google Patents

Description

Active energy ray-curable composition, cured product thereof, and article having the same

The present invention relates to an active energy ray-curable composition capable of imparting excellent scratch resistance, antifouling property, and smoothness to the surface of various articles, a cured product thereof, and an article having the cured coating film.

Since the active energy ray-curable composition has a small heat history to the applied substrate and is excellent in hardness or scratch resistance of the coating film, it is used, for example, as a plastic molding which is disadvantageous in that it is soft and the surface is easily damaged. The surface of the product imparts a scratch-resistant hard coating. Moreover, in order to impart antifouling property to the cured coating film of the active energy ray-curable composition, a fluorine compound having a perfluoropolyether group and a polymerizable group is proposed as a material to be added to the active energy ray-curable composition ( For example, refer to Patent Document 1).

However, the cured coating film of the active energy ray-curable composition containing the fluorine compound described in Patent Document 1 has excellent antifouling properties, but has a problem of poor scratch resistance or smoothness. Therefore, the industry has sought an active energy ray-curable composition capable of obtaining a cured coating film having excellent antifouling properties and excellent in scratch resistance or smoothness.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3963169

The problem to be solved by the present invention is to provide an excellent defense that can be obtained. An active energy ray-curable composition of a cured coating film which is excellent in stain resistance and scratch resistance or smoothness, a cured product thereof, and an article having the cured coating film.

The inventors of the present invention have intensively studied in order to solve the above problems, and have found that the cured coating film of the active energy ray-curable composition as described below has excellent antifouling properties and is excellent in scratch resistance or smoothness. According to the present invention, the active energy ray-curable composition contains a specific tetrafunctional or higher (meth)acrylic acid urethane, a trifunctional or higher (meth) acrylate, and a fluorine compound having a specific structure. .

That is, the present invention relates to an active energy ray-curable composition, a cured product thereof, and an article having the cured coating film thereof, wherein the active energy ray-curable composition is characterized by comprising: (meth)acrylic acid amide An ester (A) having four or more (meth) acrylonitrile groups in one molecule obtained by reacting an aliphatic polyisocyanate (a1) with a hydroxyl group-containing (meth) acrylate (a2); a functional (meth) acrylate (B) having three or more (meth) acrylonitrile groups in one molecule; and a fluorine compound (C) having the following structure, ie, poly(perfluoroalkylene) Both ends of the chain ether) chain are bonded to a cyclopentasiloxane structure via a divalent linking group, and a (meth)acryl fluorenyl group is bonded to the cyclopolyoxyalkylene structure via a divalent linking group. Further, the present invention relates to a hard coat film in which a cured product of the active energy ray-curable composition is a hard coat layer, and a protective film in which an adhesive layer is provided on the hard coat film.

The active energy ray-curable composition of the present invention is extremely useful as a hard coating agent for protecting the surface of various articles because the cured coating film has excellent antifouling properties and is excellent in scratch resistance or smoothness.

The active energy ray-curable composition of the present invention contains: (meth)acrylic acid urethane (A) which reacts an aliphatic polyisocyanate (a1) with a (meth) acrylate having a hydroxyl group (a2) And one or more (meth) acrylonitrile groups having one or more molecules; and a polyfunctional (meth) acrylate (B) having three or more (meth) acrylonitrile groups in one molecule. And a fluorine compound (C) having a structure in which a cyclopentasiloxane structure is bonded via a divalent linking group at both ends of the poly(perfluoroalkylene ether) chain, and the ring is condensed The (meth)acryl fluorenyl group is bonded to the oxyalkylene structure via a divalent linking group.

In the present invention, "(meth)acrylate" means either or both of an acrylate and a methacrylate, and "(meth)acryloyl" means a propylene group and a methacrylium group. One or both.

The (meth)acrylic acid urethane (A) has four or more molecules in one molecule obtained by reacting an aliphatic polyisocyanate (a1) with a hydroxyl group-containing (meth) acrylate (a2). Base) acrylonitrile base.

The aliphatic polyisocyanate (a1) is a compound composed of an aliphatic hydrocarbon except for an isocyanate group. Specific examples of the aliphatic polyisocyanate (a1) include aliphatic polyisocyanates (a1-1) such as hexamethylene diisocyanate, isocyanuric acid diisocyanate, and isocyanuric acid triisocyanate; Alkyl diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 1,3-bis(isocyanatemethyl)cyclohexane, 2-methyl-1,3-diisocyanate An alicyclic polyisocyanate (a1-2) such as cyclohexane or 2-methyl-1,5-diisocyanatecyclohexane. Further, a terpolymer obtained by trimerating the above aliphatic polyisocyanate (a1-1) or an alicyclic polyisocyanate (a1-2) can also be used as the above aliphatic polyisocyanate (a1). In the aliphatic polyisocyanate (a1), hexamethylene diisocyanate which is a diisocyanate of a linear aliphatic hydrocarbon, as an alicyclic diisocyanate Alkyl diisocyanate and isophorone diisocyanate are preferred because they can improve scratch resistance.

The (meth) acrylate (a2) is a compound having a hydroxyl group and a (meth) acrylonitrile group, and the above (meth) acrylate urethane (A) has four or more molecules in one molecule. The (meth) acrylonitrile group preferably has two or more (meth) acrylonitrile groups. Examples of such a (meth) acrylate (a2) include trimethylolpropane di(meth)acrylate, ethylene oxide-modified trimethylolpropane di(meth)acrylate, and a ring. Oxypropane modified trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(methyl)propenyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol Tris(meth)acrylate, di(trimethylolpropane)tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like. One type of the above-mentioned (meth) acrylate (a2) may be used alone or two or more types may be used in combination with one type of the above-mentioned aliphatic polyisocyanate (a1). Further, among the (meth) acrylates (a2), pentaerythritol tri(meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable because they can improve scratch resistance.

The reaction of the above aliphatic polyisocyanate (a1) with the above (meth) acrylate (a2) can be carried out by a conventional urethanation reaction. Further, in order to promote the progress of the urethanization reaction, it is preferred to carry out the urethanization reaction in the presence of a urethanization catalyst. Examples of the urethane-based catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; and phosphorus compounds such as triphenylphosphine and triethylphosphine; An organic tin compound such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate or tin octylate; or an organic zinc compound such as zinc octylate.

The above-mentioned (meth)acrylic acid urethane (A) obtained by the above-described urethanation reaction may be used singly or in combination of two or more kinds. Also, when two or more cases are used, the drop will be used. When an alkane diisocyanate is used as the above-mentioned aliphatic polyisocyanate (a1), the urethane urethane is used in combination with isophorone diisocyanate as the above-mentioned aliphatic polyisocyanate (a1). It is better to improve the scratch resistance.

The polyfunctional (meth) acrylate (B) is a compound having three or more (meth) acrylonitrile groups in one molecule. Specific examples of the polyfunctional (meth)acrylate (B) include trimethylolpropane tri(meth)acrylate and ethylene oxide-modified trimethylolpropane. (Meth) acrylate, propylene oxide modified trimethylolpropane tri(meth) acrylate, bis(trimethylolpropane) tri(meth) acrylate, bis(trimethylolpropane) four (meth) acrylate, tris(2-(methyl) propylene methoxyethyl) isocyanurate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri ( Methyl) acrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These polyfunctional (meth)acrylates (B) may be used alone or in combination of two or more. Moreover, in the polyfunctional (meth) acrylate (B), it is preferable to improve the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention. The propylene oxime equivalent is in the range of 50 to 200 g/eq., more preferably in the range of 70 to 150 g/eq., and further preferably in the range of 80 to 120 g/eq. Specific examples of the polyfunctional (meth) acrylate (B) having a (meth) acrylonitrile group equivalent of 80 to 200 g/eq. include pentaerythritol tetraacrylate (acrylonitrile equivalent: 88 g/eq. ), dipentaerythritol hexa(meth) acrylate (acrylonitrile equivalent: 118 g/eq.), and the like.

The mass ratio of the above (meth)acrylic acid urethane (A) to the above polyfunctional (meth)acrylate (B) in terms of improving scratch resistance [(A)/(B)] It is preferably in the range of 90/10 to 10/90, more preferably in the range of 80/20 to 20/80, and still more preferably in the range of 75/25 to 25/75.

Further, in the active energy ray-curable composition of the present invention, in addition to the above (meth)acrylic acid urethane (A) and the above polyfunctional (meth) acrylate (B), it may not be damaged. Within the scope of the effects of the present invention, a mono(meth)acrylate having one (meth)acrylinyl group in one molecule and two (meth)acrylic groups having two (meth)acrylonyl groups in one molecule are blended in one molecule. Other (meth) acrylates such as esters. When the other (meth) acrylate is blended in the active energy ray-curable composition of the present invention, the amount thereof is adjusted relative to the above-mentioned (meth)acrylic acid urethane (A) and the above polyfunctional (methyl group). The total amount of the acrylate (B) is 100 parts by mass, preferably 40 parts by mass or less, more preferably 20 parts by mass or less.

The above fluorine compound (C) is a compound having the following structure, that is, poly(perfluoroalkylene) Both ends of the chain ether) chain are bonded to a cyclopentasiloxane structure via a divalent linking group, and a (meth)acryl fluorenyl group is bonded to the cyclopolyoxyalkylene structure via a divalent linking group. Further, in the present invention, "poly(perfluoroalkylene ether)" may be referred to as "perfluoropolyether".

The poly(perfluoroalkylene ether) chain of the fluorine compound (C) includes a structure in which a divalent fluorinated carbon group having 1 to 3 carbon atoms and an oxygen atom are alternately linked. The divalent fluorinated carbon group having 1 to 3 carbon atoms may be used alone or in combination of two or more. Specific examples thereof include those represented by the following structural formula (1).

[Chemical 1]

(In the above formula (1), X is a formula (1-1) to (1-5) below, and X may be any one of the following formulae (1-1) to (1-5), and further, Two or more of the following formulae (1-1) to (1-5) may exist in a random form or in a block form. Further, n represents an integer of 2 to 200 of the repeating unit)

[Chemical 2]

-CF ₂ - (1-1)

-CF ₂ CF ₂ - (1-2)

-CF ₂ CF ₂ CF ₂ - (1-3)

The poly(perfluoroalkylene ether) chain is preferably represented by the above formula (1-1) in terms of improving the antifouling property of the cured coating film of the active energy ray-curable composition of the present invention. A poly(perfluoroalkylene ether) chain of a perfluoromethylene group in combination with a perfluoroextended ethyl group represented by the above formula (1-2). Here, the molar ratio of the perfluoromethylene group represented by the above formula (1-1) to the perfluoroethyl group represented by the above formula (1-2) [(1-1)/(1-2) ] preferably in the range of 1/10 to 10/1. Further, the value of n in the above formula (1) is preferably in the range of 2 to 200, more preferably in the range of 10 to 100, still more preferably in the range of 20 to 80.

The cyclodeoxysilane structure of the fluorine compound (C) is, for example, a structure represented by the following formula (2).

[Chemical 3]

(In the above formula (2), R ¹ is a methyl group, R ³ is a divalent organic group bonded to a poly(perfluoroalkylene ether) chain, and R ⁴ is a group having a (meth)acryl fluorenyl group. The price is organic. In addition, m is an integer from 2 to 5)

In the above cyclopentaoxane structure, a cyclotetrasiloxane having a m of 3 in the above formula (2) is preferred.

As a two-valent linkage for bonding the above poly(perfluoroalkylene ether) chain to a cyclic polyoxyalkylene structure The base group is not particularly limited as long as it is a divalent organic group, and examples thereof include those represented by the following formula (3).

[Chemical 4]

-CH ₂ -OY- (3)

(In the above formula (3), Y is an alkylene group having 1 to 6 carbon atoms)

In addition, the divalent linking group which is bonded to the (meth)acryl fluorenyl group is not particularly limited as long as it is a divalent organic group, and examples thereof include the following formula (4). Representation.

[Chemical 5]

(In the above formula (4), Z ¹ , Z ² and Z ³ are each independently an alkylene group having 1 to 6 carbon atoms)

Examples of the method for producing the fluorine compound (C) include a method of producing the fluorine compound (C) by the following steps (1) to (3).

(1) reacting a compound having an allyl group at both ends of a poly(perfluoroalkylene ether) chain with a cyclic polyoxyalkylene compound having a hydrofluorenyl group in the presence of a platinum-based catalyst to obtain a poly( The step of having a compound having a cyclic polyoxyalkylene structure at both ends of the perfluoroalkylene ether chain).

(2) a step of reacting the compound obtained in (1) with an allyloxyalkanol in the presence of a platinum-based catalyst, and adding a hydroxyl group to the cyclic polyoxyalkylene structural moiety of the compound obtained in (1) .

(3) A step of introducing a (meth) acrylonitrile group by reacting a hydroxyl group added in (2) with a (meth) acrylate having an isocyanate group.

The amount of the above fluorine compound (C) in the active energy ray-curable composition of the present invention is relative to the above (meth)acrylic acid amine in terms of sufficient scratch resistance, antifouling property and smoothness. 100 parts by mass of the urethane (A), the above polyfunctional (meth) acrylate (B), and the other (meth) acrylate optionally blended, preferably in the range of 0.05 to 5 parts by mass, more preferably It is preferably in the range of 0.1 to 2 parts by mass.

Further, the active energy ray-curable composition of the present invention can be formed into a cured coating film by applying an active energy ray after being applied to a substrate. The active energy ray refers to ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When a cured coating film is formed by irradiating ultraviolet rays as an active energy ray, it is preferred to add a photopolymerization initiator (D) to the active energy ray-curable composition of the present invention to improve the curability. Further, if necessary, a photosensitizer may be further added to improve the curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, or γ-ray is used, even if the photopolymerization initiator (D) or the photosensitizer is not used, it can be hardened quickly, so that no special addition is required. Photopolymerization initiator (D) or photo sensitizer.

Examples of the photopolymerization initiator (D) include an intramolecular cleavage type photopolymerization initiator and a dehydrogenation type photopolymerization initiator. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and oligomeric [2-hydroxy-2]. -methyl-1-[4-(1-methylvinyl)phenyl]acetone], benzoin dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2- Methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- Phytyl (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Acetophenone-based compound such as phenylphenyl)-butanone; benzoin, benzoin methyl ether, benzoin isopropyl ether, etc.; 2,4,6-trimethylbenzoin diphenylphosphine oxide, bis(2,4, a fluorenylphosphine oxide compound such as 6-trimethylbenzhydrazide)-phenylphosphine oxide; benzyl oxime, methyl phenyl glyoxylate or the like.

On the other hand, examples of the dehydrogenation type photopolymerization initiator include benzophenone, methyl phthalic acid benzoate-4-phenylbenzophenone, and 4,4'-dichlorodiphenyl. Ketone, hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, propylene benzophenone, 3,3',4,4'-tetra (peroxide Tributylcarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone Benzophenone-based compound such as ketone; 2-isopropyl-9-oxosulfur 2,4-dimethyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 9-oxosulfur Compound; amino benzophenone-based compound such as rice ketone, 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylhydrazine , 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzylidenephenylthio)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propane 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one). These photopolymerization initiators (D) may be used singly or in combination of two or more.

Further, examples of the photosensitizer include a tertiary amine compound such as diethanolamine, N-methyldiethanolamine or tributylamine, a urea compound such as o-tolylthiourea, and sodium diethyldithiophosphate. And sulfur compounds such as s-benzylisothiourea p-toluenesulfonate.

The amount of the photopolymerization initiator and the photosensitizer to be used is preferably 0.05 to 20 parts by mass, more preferably 0.05 to 20 parts by mass, per 100 parts by mass of the non-volatile component in the active energy ray-curable composition of the present invention. 0.5 to 10% by mass.

Further, in the active energy ray-curable composition of the present invention, in addition to the above components (A) to (D), a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, and a viscosity adjustment may be formulated as needed. Agents, light stabilizers, weather stabilizers, heat stabilizers, UV absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, cerium oxide beads, organic beads, etc.; An inorganic filler such as alumina, titania, zirconia or pentoxide. These other formulations may be used singly or in combination of two or more.

As a method of applying the active energy ray-curable composition of the present invention to a substrate, Depending on the application, for example, die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, and contact coating (kiss coat) ), spray coating, erection coating, dip coating, spin coating, wheeler coating, brush coating, solid coating using a silk screen, wire coating, flow Painted and so on.

As described above, the active energy ray for curing the active energy ray-curable composition of the present invention is an ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays, as a specific irradiation active energy ray. In the case of using ultraviolet rays, as a source of ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an electrodeless lamp (Fusion Lamp), a chemical lamp, a black lamp can be cited. , mercury - xenon lamp, short arc lamp, cadmium cadmium laser, argon laser, sunlight, LED, etc. Further, when the substrate to which the active energy ray-curable composition of the present invention is applied is a film substrate, if a xenon flash lamp which is irradiated with a flash is used, the influence of heat on the film substrate can be reduced, so that good. On the other hand, in the case of using an electron beam, as a generation source of the electron beam, a scanning electron beam accelerator, a curtain type electron beam accelerator, or the like can be cited.

Further, when the active energy ray-curable composition of the present invention is irradiated with ultraviolet rays to form a cured coating film, it can be obtained in an air atmosphere, and a cured coating film having more excellent scratch resistance and smoothness can be obtained. In particular, it is preferably carried out in an environment having an oxygen concentration of 5,000 ppm or less.

Since the cured coating film of the active energy ray-curable composition of the present invention has excellent antifouling properties and is excellent in scratch resistance or smoothness, the active energy ray-curable composition of the present invention is applied to various types. The surface of the article is hardened, and it is possible to impart excellent antifouling properties, scratch resistance, and smoothness to the surfaces of various articles. Therefore, the active energy ray-curable composition of the present invention can be used as a hard coating agent having antifouling properties.

Examples of the article to which the active energy ray-curable composition of the present invention can be applied include a casing of a home electric appliance such as a television, a refrigerator, a washing machine, and an air conditioner; The outer casing of electronic devices such as smart phones, mobile phones, digital cameras, game consoles, etc.; interior materials for various vehicles such as automobiles and railway vehicles; various building materials such as decorative panels; woodworking materials such as furniture, and labor. Synthetic leather; FRP bath; optical film of liquid crystal display (LCD) such as triacetyl cellulose (TAC) film; enamel or diffuser as backlight member of LCD; various displays such as plasma display (PDP), organic EL display Screen (hard coating, anti-reflection layer); touch panel; screen of electronic terminals such as mobile phones and smart phones; transparent protective film for color filters for liquid crystal displays (hereinafter referred to as "CF"); CD, DVD , optical recording media such as Blu-ray Disc; transfer film for injection molding (IMD, IMF); rubber for OA equipment (Office Automation Equipment) such as photocopying machine and printer Roller; glass surface of the reading part of OA equipment such as photocopiers, scanners; optical lenses of cameras, video cameras, glasses, etc.; windshields and glass surfaces of watches and other watches; windows of various vehicles such as automobiles and railway vehicles; Solar glass, cover glass or cover film; various building materials such as decorative panels; window glass for houses; woodworking materials such as furniture.

The hard coat film of the present invention has a hard coat layer obtained by curing the active energy ray-curable composition of the present invention on at least one side of the film substrate. As the film substrate, various resin film substrates which are generally used can be used, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, and polypropylene. , 赛璐凡, 醯 醯 cellulose, triacetonitrile cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymer, cyclic olefin copolymer, polyvinyl chloride, Polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polyfluorene, polyetheretherketone, polyether oxime, polyetherimide, A resin film such as polyimide, fluororesin, nylon, or acrylic resin. In particular, a resin film of polyethylene terephthalate, triacetyl cellulose, or an acrylic resin is preferably used because it is excellent in transparency and workability.

Further, the film substrate may be a substrate composed only of the above-exemplified resin film, or may be A film substrate provided with an undercoat layer on the resin film to improve adhesion to the active energy ray-curable composition of the present invention. Examples of the undercoat layer include a polyester resin, an urethane resin, and an acrylic resin. Further, for the purpose of improving the adhesion to the hard coat layer, the surface of the blasting method, the solvent treatment method, etc., the surface roughening treatment, the corona discharge treatment, the chromic acid treatment, the flame treatment, the hot air treatment, the ozone. The surface of the resin film is treated by ultraviolet irradiation treatment, oxidation treatment, or the like.

Further, the thickness of the film substrate is preferably in the range of 50 to 200 μm, more preferably in the range of 80 to 150 μm, still more preferably in the range of 90 to 130 μm. In the present invention, by setting the thickness of the film substrate to this range, it is easy to suppress curl even when a hard coat layer is provided on one surface of the film substrate.

Further, as the film substrate, a film substrate having a modulus of elasticity of 3 to 7 GPa is preferably used, and a film substrate having a range of 3 to 5 GPa is particularly preferably used. When the modulus of elasticity is in this range, deformation of the film substrate is less likely to occur when the protective film is formed, and cracking of the hard coat layer can be suppressed, and it is easy to suppress a decrease in hardness of the surface of the hard coat film. Moreover, since the flexibility of the film substrate can be ensured, it is easy to follow the gentle curved surface when the protective film is attached as described later.

The protective film of the present invention is one in which an adhesive layer is provided on one surface of the above hard coat film. The adhesive layer may be provided by attaching an adhesive tape to the film substrate, or by directly applying an adhesive layer on a surface of the film substrate opposite to the hard coating surface.

The thickness of the adhesive layer of the protective film of the present invention is preferably in the range of 5 to 50 μm, more preferably in the range of 8 to 30 μm, still more preferably in the range of 10 to 25 μm. In the present invention, by setting the thickness of the pressure-sensitive adhesive layer to the above range, it is possible to provide excellent adhesion reliability and maintain the surface hardness of the hard coat film without being significantly impaired.

As the adhesive for the adhesive layer used in the present invention, a known acrylic resin, rubber-based or polyoxynoxy-based adhesive resin can be used. Among them, from the viewpoint of adhesion to the film substrate, transparency, and weather resistance, it is preferred to use a (meth) acrylate monomer having an alkyl group having 2 to 14 carbon atoms as a repeating unit as a main component. Propylene polymerized from components Acid copolymer.

Examples of the (meth) acrylate monomer having 2 to 14 carbon atoms include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, second butyl acrylate, and acrylic acid. Butyl ester, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, isodecyl acrylate, lauryl acrylate, methyl methacrylate, Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, second butyl methacrylate, third butyl methacrylate, n-hexyl methacrylate, A Cyclohexyl acrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, isodecyl methacrylate, lauryl methacrylate, etc. .

Among the above (meth) acrylate monomers, an alkyl (meth) acrylate having an alkyl group having 4 to 9 carbon atoms is preferred, and more preferably an alkyl group having 4 to 9 carbon atoms. Alkyl acrylate. Among the alkyl acrylates, n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and ethyl acrylate are particularly preferred. By using an alkyl (meth)acrylate having an alkyl group having a carbon number in the range, it is easy to ensure a suitable adhesion.

The content of the (meth) acrylate having 2 to 14 carbon atoms in the monomer constituting the acrylic copolymer used in the adhesive layer of the present invention is preferably 90 to 99% by mass, more preferably 90 to 96% by mass. %. By setting the content of the above (meth) acrylate to the above range, it is easy to ensure a suitable adhesive force.

In the acrylic copolymer, a (meth) acrylate monomer having a polar group such as a hydroxyl group, a carboxyl group or a guanamine group, or a vinyl monomer having another polar group is preferably used as a monomer component.

Examples of the (meth) acrylate monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. , hydroxypropyl (meth) acrylate, caprolactone modified (meth) acrylate, polyethylene glycol Mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like. Among these, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate are preferably used.

Examples of the (meth) acrylate monomer having a carboxyl group include a dimer of acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, acrylic acid or methacrylic acid, and epoxy. Ethane modified succinic acid acrylate or the like. Among these, acrylic acid is preferably used.

Examples of the (meth) acrylate monomer having a guanamine group include N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and propylene oxime. Porphyrin, acrylamide, N,N-dimethylpropenamide, 2-(perhydrophthalic acid imine-N-yl)ethyl acrylate, and the like. Among these, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, and propylene oxime are preferably used. Porphyrin.

Examples of the vinyl monomer having another polar group include vinyl acetate, acrylonitrile, maleic anhydride, and itaconic anhydride.

The content of the monomer having a polar group is preferably from 0.1 to 20% by mass, more preferably from 1 to 13% by mass, even more preferably from 1.5 to 8% by weight, based on the monomer component constituting the acrylic copolymer. By including a monomer having a polar group in this range, it is easy to adjust the cohesive force, the holding power, and the adhesion of the adhesive to a suitable range.

The weight average molecular weight Mw of the acrylic copolymer used in the adhesive layer is preferably from 400,000 to 1,400,000, more preferably from 600,000 to 1,200,000. When the weight average molecular weight Mw of this acrylic copolymer is in this range, it is easy to adjust an adhesive force to a specific range.

Further, the above weight average molecular weight Mw can be measured by gel permeation chromatography (GPC). More specifically, "SC8020" manufactured by Tosoh Corporation can be used as a GPC measuring device, and can be obtained by measuring the polystyrene-converted value under the following GPC measurement conditions.

(Measurement conditions for GPC)

. Sample concentration: 0.5% by weight (tetrahydrofuran solution)

. Sample injection amount: 100 μL

. Dissolved solution: tetrahydrofuran (THF)

. Flow rate: 1.0mL/min

. Column temperature (measuring temperature): 40 ° C

. Pipe column: "TSKgel GMHHR-H" made by Tosoh Corporation

. Detector: differential refraction

Further, in order to increase the cohesive force of the adhesive layer, it is preferred to add a crosslinking agent to the adhesive. Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, and a chelate crosslinking agent. The amount of the crosslinking agent to be added is preferably adjusted so that the gel fraction of the adhesive layer is 25 to 80% by mass, more preferably 40 to 75% by mass, and most preferably Adjust to 50 to 70% by mass. By adjusting the gel fraction to this range, it is possible to suppress a decrease in the surface pencil hardness when the protective film is attached to the substrate, and it is also possible to sufficiently improve the adhesion. Further, in the gel fraction of the present invention, the cured adhesive layer was immersed in toluene, and the mass of the insoluble component remaining after leaving for 24 hours was measured, and the mass was expressed as a percentage with respect to the original mass.

Further, in order to increase the adhesion of the adhesive layer, an adhesion-imparting resin may be added. When the adhesive resin is an acrylic copolymer, it is preferably added in an amount of 10 to 60 parts by mass based on 100 parts by mass of the acrylic copolymer. Further, when the adhesion is important, it is preferably added in the range of 20 to 50 parts by mass.

Further, in addition to the above, an additive known in the art may be added to the adhesive. For example, in order to improve the adhesion to the glass substrate, it is preferred to add the decane coupling agent in an amount of 0.001 to 0.005 parts by mass based on 100 parts by mass of the adhesive. Further, a plasticizer, a softener, a filler, a pigment, a flame retardant or the like as another additive may be added as needed.

Since the protective film of the present invention has excellent scratch resistance or smoothness, it can be suitably used for various purposes, and is particularly preferably applied to an image display portion of an image display device such as a liquid crystal display (LCD) or an organic EL display. In particular, even if it is thin, it can achieve better scratch resistance or smoothness, so it is suitable for miniaturization of electronic notebooks, mobile phones, smart phones, portable audio players, mobile personal computers, tablet terminals, etc. A protective film for an image display portion of an image display device of a portable electronic terminal having a relatively high thickness. For example, the image display device includes an image display module such as an LCD module or an organic EL module, and the image display module is provided with an upper portion for protecting the image display. The image display device of the transparent panel of the module is used by being attached to the front or back surface of the transparent panel, thereby preventing damage or preventing scattering of the transparent panel when it is broken.

[Examples]

The invention will be more specifically described below by way of examples.

(Synthesis Example 1: Synthesis of urethane acrylate (A1))

A mixture of pentaerythritol triacrylate (hereinafter referred to as "PE3A") and pentaerythritol tetraacrylate (hereinafter referred to as "PE4A") is added to a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer (PE3A/PE4A=60/). 40 (mass ratio) of 549.1 parts by mass, 0.1 parts by mass of dibutyltin diacetate, 0.6 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of p-methoxyphenol, and 160 parts by mass of butyl acetate, and air was blown evenly. The mixing side slowly heats up. After reaching 60 ° C, 90.9 parts by mass of hexamethylene diisocyanate was added, and then reacted at 80 ° C for 5 hours to obtain a urethane amide (A1) having 6 propylene groups in one molecule. The volatile component was a solution of 80% by mass. Further, in the solution, the nonvolatile component contained 34.3% by mass of PE4A in addition to the acrylamide amide (A1).

(Synthesis Example 2: Synthesis of urethane acrylate (A2))

Adding 250 parts by mass of butyl acetate to a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer 206 parts by mass of alkane diisocyanate, 0.5 parts by mass of p-methoxyphenol and 0.5 parts by mass of dibutyltin diacetate were heated to 70 ° C while blowing air, and then a mixture of PE3A and PE4A was added dropwise over 1 hour (PE3A/PE4A= 75/25 (mass ratio)) 795 parts by mass. After completion of the dropwise addition, the reaction was carried out at 70 ° C for 3 hours, and the reaction was further carried out until the infrared absorption spectrum of 2250 cm ^-1 of the isocyanate group disappeared, and an amino amide having 6 acryl groups in one molecule was obtained. The nonvolatile component of the ester (A2) was a 80% by mass solution of butyl acetate. Further, in the solution, the nonvolatile component contained 19.9% by mass of PE4A in addition to the urethane urethane (A2).

(Synthesis Example 3: Synthesis of urethane acrylate (A3))

254 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate, 0.5 parts by mass of p-methoxyphenol, and 0.5 parts by mass of dibutyltin diacetate were placed in a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer. The temperature was raised to 70 ° C while blowing air, and then a mixture of PE3A and PE4A (PE3A/PE4A = 75/25 (mass ratio)) of 795 parts by mass was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was carried out at 70 ° C for 3 hours, and the reaction was further carried out until the infrared absorption spectrum of 2250 cm ^-1 of the isocyanate group disappeared, and an amino amide having 6 acryl groups in one molecule was obtained. The nonvolatile component of the ester (A3) was a solution of 80% by mass. Further, in the solution, the nonvolatile component contained 19.5% by mass of PE4A in addition to the acrylamide amide (A3).

(Synthesis Example 4: Synthesis of urethane acrylate (A4))

254 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate, 0.5 parts by mass of p-methoxyphenol, and 0.5 parts by mass of dibutyltin diacetate were placed in a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer. The temperature was raised to 70 ° C while blowing air, and then 369 parts by mass of bis(2-propenyloxyethyl) isocyanurate and a mixture of PE3A and PE4A were added dropwise over 1 hour (PE3A/PE4A=75). /25 (mass ratio)) 398 parts by mass. After completion of the dropwise addition, the reaction was carried out at 70 ° C for 3 hours, and the reaction was further carried out until the infrared absorption spectrum of 2250 cm ^-1 of the isocyanate group disappeared, and an amine amide group having 4 to 6 propylene groups in one molecule was obtained. The nonvolatile component of the formate (A4) was a solution of 80% by mass. Further, in the solution, the nonvolatile component contained 10.1% by mass of PE4A in addition to the acrylamide amide (A4).

(Synthesis Example 5: Synthesis of urethane acrylate (A5))

A mixture of PE3A and PE4A (PE3A/PE4A=60/40 (mass ratio)) 242 parts by mass, p-methoxyphenol 0.23 parts by mass, and dilauric acid were added to a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer. 0.13 parts by mass of dibutyltin and 100 parts by mass of methyl ethyl ketone, and the temperature was raised to 75 ° C while blowing air, and then a trimer of hexamethylene diisocyanate (isocyanurate) was added dropwise over 2 hours ( "Desmodur N3390BA" manufactured by Sumika Bayer Urethane Co., Ltd., a non-volatile component of 90% by mass, NCO%: 19.6, NCO equivalent: 214 g/eq.) 107 parts by mass and 50 parts by mass of methyl ethyl ketone . After completion of the dropwise addition, the reaction was carried out at 75 ° C for 4 hours, and further, the reaction was carried out until the infrared absorption spectrum of 2250 cm ^-1 of the isocyanate group disappeared, and an amino amide having 9 propylene groups in one molecule was obtained. The nonvolatile component of the ester (A5) was a solution of 67.8% by mass. Further, in the solution, the nonvolatile component contained 28.6% by mass of PE4A in addition to the acrylamide urethane (A5).

(Synthesis Example 6: Synthesis of urethane acrylate (A6))

A mixture of dipentaerythritol pentaacrylate (hereinafter abbreviated as "DPPA") and dipentaerythritol hexaacrylate (hereinafter abbreviated as "DPHA") (DPPA/) is added to a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer. DPHA=60/40 (mass ratio)) 436.7 parts by mass, 0.23 parts by mass of p-methoxyphenol, 0.13 parts by mass of dibutyltin dilaurate, and 180 parts by mass of methyl ethyl ketone, and the temperature was raised to 75 ° C while blowing air. Then, a terpolymer (isocyanurate) of isophorone diisocyanate (Desmodur Z4470BA, manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise over 2 hours, and the nonvolatile content was 70% by mass, NCO%. : 11.7, NCO equivalent: 359 g/eq.) 180 parts by mass and a mixed solution of 80 parts by mass of methyl ethyl ketone (hereinafter abbreviated as "MEK"). After completion of the dropwise addition, the reaction was carried out at 75 ° C for 4 hours, and further the reaction was carried out until the infrared absorption spectrum of 2250 cm ^-1 of the isocyanate group disappeared, and an amino amide having 15 propylene groups in one molecule was obtained. The nonvolatile component of the ester (A5) was a solution of 64.2% by mass. Further, in the solution, the nonvolatile component contained 31% by mass of DPHA in addition to the acrylamide amide (A6).

(Synthesis Example 7: Synthesis of urethane acrylate (RA1))

58.4 parts by mass of 2-hydroxypropyl acrylate, 0.23 parts by mass of p-methoxyphenol, 0.13 parts by mass of dibutyltin dilaurate, and methyl ethyl ketone 100 were placed in a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer. The mass fraction was heated to 60 ° C while blowing air, and then a trimer of hexamethylene diisocyanate (isocyanurate) was added dropwise over 2 hours (Desmodur N3390BA, manufactured by Sumika Bayer Urethane Co., Ltd.). A non-volatile component: 90% by mass, NCO%: 19.6, NCO equivalent: 214 g/eq.), a mixed solution of 107 parts by mass and 50 parts by mass of methyl ethyl ketone. After completion of the dropwise addition, the reaction was carried out at 60 ° C for 4 hours, and the reaction was further carried out until the infrared absorption spectrum of 2250 cm ^-1 of the isocyanate group disappeared, and an amino amide having 3 propylene groups in one molecule was obtained. The nonvolatile component of the ester (RA1) was a solution of 71.8% by mass.

(Synthesis Example 8: Synthesis of Polymer (E1))

250 parts by mass of glycidyl methacrylate, 1.3 parts by mass of lauryl mercaptan, 1,000 parts by mass of methyl isobutyl ketone, and 2,2'-azo were added to a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer. 7.5 parts by mass of bisisobutyronitrile was heated to 90 ° C over 1 hour while stirring under a nitrogen gas stream, and allowed to react at 90 ° C for 1 hour. Then, while stirring at 90 ° C, a mixture of 750 parts by mass of glycidyl methacrylate, 3.7 parts by mass of lauryl mercaptan, and 22.5 parts by mass of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. Thereafter, the mixture was reacted at 100 ° C for 3 hours. Then, adding 2,2'-azobisisobutyronitrile 10 The mass fraction was further reacted at 100 ° C for 1 hour, and then the temperature was raised to around 120 ° C to carry out a reaction for 2 hours. After cooling to 60 ° C, the nitrogen gas introduction tube was replaced with an air introduction tube, and 507 parts by mass of acrylic acid, 2 parts by mass of p-methoxyphenol, and 5.4 parts by mass of triphenylphosphine were added, and the reaction liquid was foamed while using air. The temperature was raised to 110 ° C and allowed to react for 8 hours. Then, 1.4 parts by mass of p-methoxyphenol was added, and after cooling to room temperature, methyl isobutyl ketone was added in such a manner that the nonvolatile component became 50% by mass to obtain an acrylic resin having an acrylonitrile group, that is, a polymer ( Solution of E1). Further, the obtained polymer (E1) had a weight average molecular weight of 31,000 (polystyrene equivalent value obtained by GPC) and an acrylonitrile equivalent of 300 g/eq.

(Synthesis Example 9: Synthesis of fluorine compound (C1))

To a flask equipped with a stirrer and a cooling tube, 500 parts by mass of perfluoropolyether having an allyl group represented by the following formula (5) and m-bis(trifluorotoluene) (m-) were added to a flask equipped with a stirrer and a cooling tube. Xylene hexafluoride) (700 parts by mass and 361 parts by mass of tetramethylcyclotetraoxane) were heated to 90 ° C while stirring. 0.442 parts by mass of a toluene solution of a chloroplatinic acid/vinyl siloxane complex (containing 1.1×10 ^-6 mols in terms of Pt simple substance) was added thereto, and the internal temperature was maintained at 90 ° C or higher. 4 hours. After confirming the disappearance of the allyl group of the raw material in the ¹ H-NMR spectrum, the solvent or excess tetramethylcyclotetraoxane was distilled off under reduced pressure to carry out activated carbon treatment, thereby obtaining the following formula (6). The colorless transparent liquid is a perfluoropolyether compound (1).

[Chemical 6]

H ₂ C=CHCH ₂ OCH ₂ -Rf-CH ₂ OCH ₂ CH=CH ₂ (5)

Rf:

(where m/n is 0.9, and the total of m and n is an average of 45)

[Chemistry 7]

50 parts by mass of the perfluoropolyether compound (1) obtained above, 7.05 parts by mass of 2-allyloxyethanol, 50 parts by mass of m-bis(trifluorotoluene), and platinum chloride acid/in a dry air atmosphere. 0.0442 parts by mass of a toluene solution of a vinyl oxane complex (containing 1.1 × 10 ^-7 mols in terms of Pt simple substance), and stirred at 100 ° C for 4 hours. After confirming the disappearance of the Si—H group in the ¹ H-NMR spectrum and the infrared absorption spectrum, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure to carry out activated carbon treatment, whereby the following formula (7) was obtained. The pale yellow transparent liquid represented by the perfluoropolyether compound (2).

[化8]

50 parts by mass of the perfluoropolyether compound (2) obtained above, 50 parts by mass of tetrahydrofuran, and 9 parts by mass of 2-propenyloxyethyl isocyanate were mixed in a dry air atmosphere, and heated to 50 °C. Then, 0.05 parts by mass of dioctyltin laurate was added, and the mixture was stirred at 50 ° C for 24 hours. After completion of the heating, the mixture was removed under reduced pressure at 80 ° C and 0.27 kPa to obtain a pale yellow paste-like fluorine compound (C1) represented by the following formula (8). To the fluorine compound (C1) A mixed solvent of methyl ethyl ketone and methyl isobutyl ketone (methyl ethyl ketone / methyl isobutyl ketone = 1/3 (mass ratio)) was added, and the nonvolatile component was prepared to be 20% by mass. Fluorine compound (C1) solution.

[Chemistry 9]

Using the urethane urethanes (A1) to (A6), (RA1), the polymer (E1) and the fluorine compound (C1) obtained above, an active energy ray-curable composition was prepared as follows.

(Example 1)

31.3 parts by mass of a solution containing acrylamide (A2) obtained in Synthesis Example 2 (containing 20 parts by mass of urethane amide (A2), and 5 parts by mass of PE4A), and the product obtained in Synthesis Example 3 was contained. 31.3 parts by mass of a solution of urethane acrylate (A3) (containing 20.1 parts by mass of urethane acrylate (A3), 4.9 parts by mass of PE4A), and acrylamide containing acrylate obtained in Synthesis Example 4 (A4) 25 parts by mass of the solution (containing 18 parts by mass of urethane amide (A4), 2 parts by mass of PE4A), a mixture of DPHA and DPPA (DPHA/DPPA = 60/40 (mass ratio)), 30 parts by mass, fluorine 1.5 parts by mass of a 20% by mass solution of the compound (C1) (0.3 parts by mass based on the fluorine compound (C1)) and a photopolymerization initiator (IRGACURE 184, manufactured by BASF JAPAN Co., Ltd., 1-hydroxycyclohexylbenzene) The base ketone; hereinafter referred to as "photopolymerization initiator (D1)"), after uniformly stirring 4.5 parts by mass, was diluted with ethyl acetate to prepare an active energy ray-curable composition having a nonvolatile content of 40% by mass ( 1).

[Evaluation of the appearance of the paint]

In order to judge that the active energy ray-curable composition (1) obtained above can be used as a coating The appearance of the paint was evaluated by visual observation of the appearance according to the following criteria.

○: No white turbidity and separation of components.

×: There is white turbidity or separation of components.

[Production of test film]

The active energy ray-curable composition (1) obtained above was applied to a polyethylene terephthalate film (COSMOSHINE A4100, manufactured by Toyobo Co., Ltd., thickness: 100 μm) using a wire bar (#40). After drying at 60 ° C for 1 minute on the easy-to-handle surface, an ultraviolet irradiation device ("MIDN-042-C1" manufactured by Eyegraphics Co., Ltd., lamp: 120 W/cm, high-pressure mercury lamp) was used in an air atmosphere. The amount of irradiation light was 0.5 J/cm ^{2 and} ultraviolet rays were irradiated to obtain a test piece film having a cured coating film (hard coat layer) having a thickness of 10 μm.

[Evaluation of the appearance of hardened film]

The surface of the cured coating film of the test piece film obtained above was visually observed, and the appearance of the cured coating film was evaluated based on the following criteria.

○: No coating unevenness, coating streaks, and agglomeration.

△: There was a small amount of coating unevenness, coating streaks or agglomeration.

×: There is uneven coating, coating streaks or agglomeration.

The test piece film obtained above was subjected to evaluation or measurement of the following scratch resistance, water contact angle, mark ink repellency, and smoothness.

[Evaluation of scratch resistance]

The test piece film obtained above was cut into a rectangular shape of 30 cm × 2 cm, and fixed by a jig to a flat friction tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), using steel wool #0000, with a load of 2 kg/cm ² , stroke (stroke) The test piece was circulated 2000 times at 10 cm and a speed of 20 cm/s, and the damage state of the test piece after the execution was visually observed, and the scratch resistance was evaluated based on the following criteria.

◎: No damage.

○: The damage did not reach 5 pieces.

△: Although there were five or more damages, the entire surface of the test piece film was not damaged.

×: The entire test piece film was damaged.

[Measurement of water contact angle]

The test piece film obtained above was cut into a rectangular shape of 1 × 5 cm, and the hardened coating film of the test piece film was used as the front side, and the glass plate was fixed by a double-sided tape, and the automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd. was used. DROMP AMS TER500" measures the contact angle of 4 to 4.5 μL of purified water.

[Evaluation of antifouling properties]

On the hardened coating film of the test piece film obtained above, the ink was applied in a circular shape by "UniMediax (black)" manufactured by Mitsubishi Pencil Co., Ltd., and the degree of repulsion of the ink was visually observed. Based on this observation, the antifouling property was evaluated based on the following criteria.

5: Repels the ink in a dot shape.

4: Repel ink in dots and lines.

3: Repels the ink in a line.

2: Slightly reject the ink.

1: Does not reject ink.

[Evaluation of surface smoothness]

The surface of the cured coating film of the test piece film obtained above was wiped by BEMCOT (made by Asahi Kasei Fiber Co., Ltd.), and the smoothness was evaluated based on the following criteria based on the degree of slippage at this time.

◎: Extremely easy to slide

○: Sliding

△: not easy to slide

×: does not slide

(Example 2)

22.5 parts by mass of the solution containing the urethane urethane (A2) obtained in Synthesis Example 2 (containing 14.4 parts by mass of acrylamide (A2), 3.6 parts by mass of PE4A), and the product obtained in Synthesis Example 3 was contained. 22.5 parts by mass of a solution of urethane acrylate (A3) (containing 14.5 parts by mass of urethane acrylate (A3), 3.5 parts by mass of PE4A), and acrylamide containing acrylate obtained in Synthesis Example 4 (A4) 17.5 parts by mass of the solution (containing 12.6 parts by mass of urethane acrylate (A4), 1.4 parts by mass of PE4A), a mixture of DPHA and DPPA (DPHA/DPPA = 60/40 (mass ratio)), 50 parts by mass, fluorine 1.5 parts by mass of a 20% by mass solution of the compound (C1) (0.3 parts by mass based on the fluorine compound (C1)) and 4.5 parts by mass of the photopolymerization initiator (D1) were uniformly stirred, and then diluted with ethyl acetate to prepare. The active energy ray-curable composition (2) having a nonvolatile content of 40% by mass. Using the obtained active energy ray-curable composition (2), a test piece film was produced in the same manner as in Example 1, and then the appearance of the coating agent, the appearance of the cured coating film, the scratch resistance, the water contact angle, and the antifouling property were evaluated or measured. Smoothness.

(Example 3)

87.5 parts by mass of a solution containing the urethane amide (A1) obtained in Synthesis Example 1 (containing 46 parts by mass of urethane amide (A1), 24 parts by mass of PE4A), a mixture of DPHA and DPPA (DPHA) /DPPA = 60 / 40 (mass ratio)) 30 parts by mass, a fluorine compound (C1) 20 mass% solution 1.5 parts by mass (0.3 parts by mass based on the fluorine compound (C1)) and a photopolymerization initiator (D1) 4.5 parts by mass of the mixture was uniformly stirred, and then diluted with ethyl acetate to prepare an active energy ray-curable composition (3) having a nonvolatile content of 40% by mass. Using the obtained active energy ray-curable composition (3), a test piece film was produced in the same manner as in Example 1, and then the appearance of the coating agent, the appearance of the cured coating film, the scratch resistance, the water contact angle, and the antifouling property were evaluated or measured. Smoothness.

(Example 4)

62.5 parts by mass of a solution containing the urethane amide (A1) obtained in Synthesis Example 1 (containing 32.8 parts by mass of urethane acrylate (A1), 17.2 parts by mass of PE4A), a mixture of DPHA and DPPA (DPHA) /DPPA=60/40 (mass ratio)) 50 parts by mass, fluorinated 1.5 parts by mass of a 20% by mass solution of the compound (C1) (0.3 parts by mass based on the fluorine compound (C1)) and 4.5 parts by mass of the photopolymerization initiator (D1) were uniformly stirred, and then diluted with ethyl acetate. An active energy ray-curable composition (4) having a nonvolatile component of 40% by mass was prepared. Using the obtained active energy ray-curable composition (4), a test piece film was produced in the same manner as in Example 1, and then the appearance of the coating agent, the appearance of the cured coating film, the scratch resistance, the water contact angle, and the antifouling property were evaluated or measured. Smoothness.

(Example 5)

43.8 parts by mass of a solution containing acrylamide (A3) obtained in Synthesis Example 3 (containing 28.2 parts by mass of urethane acrylate (A3), 6.8 parts by mass of PE4A), a mixture of DPHA and DPPA (DPHA) /DPPA=60/40 (mass ratio)) 50 parts by mass, 15 parts by mass of hexanediol diacrylate (hereinafter abbreviated as "HDDA"), and 15 parts by mass of a fluorine compound (C1) solution of 1.5 parts by mass (as a fluorine compound) (C1) is 0.3 parts by mass) and 4.5 parts by mass of the photopolymerization initiator (D1) are uniformly stirred, and then diluted with ethyl acetate to prepare an active energy ray-curable composition having a nonvolatile content of 40% by mass. (5). Using the obtained active energy ray-curable composition (5), a test piece film was produced in the same manner as in Example 1, and then the appearance of the coating agent, the appearance of the cured coating film, the scratch resistance, the water contact angle, and the antifouling property were evaluated or measured. Smoothness.

(Example 6)

56.3 parts by mass of the solution containing the urethane amide (A3) obtained in Synthesis Example 3 (containing 36.2 parts by mass of urethane amide (A3), 8.8 parts by mass of PE4A), and the product obtained in Synthesis Example 5 was contained. 36.9 parts by mass of a solution of urethane acrylate (A5) (containing 17.8 parts by mass of urethane acrylate (A5), 7.2 parts by mass of PE4A), a mixture of PE4A and PE3A (PE4A/PE3A=60/40 (quality) 30 parts by mass, 1.5 parts by mass of a 20% by mass solution of the fluorine compound (C1) (0.3 parts by mass based on the fluorine compound (C1)), and 4.5 parts by mass of the photopolymerization initiator (D1) are uniformly stirred, and then used. Ethyl acetate was diluted to prepare an active energy ray-curable composition (6) having a nonvolatile content of 40% by mass. Use of the obtained active energy In the strand curable composition (6), a test piece film was produced in the same manner as in Example 1, and the appearance of the coating agent, the appearance of the cured coating film, the scratch resistance, the water contact angle, the antifouling property, and the smoothness were evaluated or measured.

(Example 7)

56.3 parts by mass of the solution containing the urethane urethane (A3) obtained in Synthesis Example 3 (containing 36.2 parts by mass of urethane urethane (A3), 8.8 parts by mass of PE4A), and the product obtained in Synthesis Example 6 was contained. 38.9 parts by mass of a solution of urethane acrylate (A6) (containing 17.2 parts by mass of urethane acrylate (A6), 7.8 parts by mass of DPHA), a mixture of PE4A and PE3A (PE4A/PE3A=60/40 (quality) 30 parts by mass, 1.5 parts by mass of a 20% by mass solution of the fluorine compound (C1) (0.3 parts by mass based on the fluorine compound (C1)), and 4.5 parts by mass of the photopolymerization initiator (D1) are uniformly stirred, and then used. Ethyl acetate was diluted to prepare an active energy ray-curable composition (7) having a nonvolatile content of 40% by mass. Using the obtained active energy ray-curable composition (7), a test piece film was produced in the same manner as in Example 1, and then the appearance of the coating agent, the appearance of the cured coating film, the scratch resistance, the water contact angle, and the antifouling property were evaluated or measured. Smoothness.

(Example 8)

In the same manner as in the first embodiment, the active energy ray-curable composition (1) obtained in Example 1 was changed to an environment having an oxygen concentration of 5,000 ppm or less in the case where the test sheet film was cured. The appearance, the scratch resistance, the water contact angle, the antifouling property, and the smoothness of the cured coating film were evaluated or measured.

(Example 9)

In the same manner as in the first embodiment, the active energy ray-curable composition (2) obtained in Example 2 was changed to an environment having an oxygen concentration of 5,000 ppm or less in the case where the test piece film was used. The appearance, the scratch resistance, the water contact angle, the antifouling property, and the smoothness of the cured coating film were evaluated or measured.

(Comparative Example 1)

In place of the fluorine compound (C1) used in the first embodiment, a fluorine compound having an acrylonitrile group at a single terminal of a poly(perfluoroalkylene ether) chain ("OPTOOL DAC-HP" manufactured by Daikin Industries Co., Ltd." In the same manner as in Example 1, except that the nonvolatile component was used in the same manner as in Example 1 except that the amount of the nonvolatile component was 20 parts by mass, and the amount of the fluorine compound (RC1) was 1.5 parts by mass (hereinafter referred to as 0.3 parts by mass based on the fluorine compound (RC1)). An active energy ray-curable composition (R1) was obtained. Using the obtained active energy ray-curable composition (R1), a test piece film was produced in the same manner as in Example 1, and then the appearance of the coating agent, the appearance of the cured coating film, the scratch resistance, the water contact angle, and the antifouling property were evaluated or measured. Smoothness.

(Comparative Example 2)

180 parts by mass of a solution of the polymer (E1) obtained in Synthesis Example 8, a mixture of DPHA and DPPA (DPHA/DPPA = 60/40 (mass ratio)), 10 parts by mass, and a 20% by mass solution of the fluorine compound (C1) 1.5 parts by mass (0.3 parts by mass based on the fluorine compound (C1)) and 4.5 parts by mass of the photopolymerization initiator (D1) were uniformly stirred, and then diluted with ethyl acetate to prepare a nonvolatile component of 40% by mass. Active energy ray-curable composition (R2). Using the obtained active energy ray-curable composition (R2), a test piece film was produced in the same manner as in Example 1, and then the appearance of the coating agent, the appearance of the cured coating film, the scratch resistance, the water contact angle, and the antifouling property were evaluated or measured. Smoothness.

(Comparative Example 3)

97.5 parts by mass of a solution containing acrylamide (RA1) obtained in Synthesis Example 7 (70 parts by mass based on urethane amide (RA1)), a mixture of DPHA and DPPA (DPHA/DPPA= 30 parts by mass of 60/40 (mass ratio), 1.5 parts by mass of a 20% by mass solution of a fluorine compound (C1) (0.3 parts by mass based on the fluorine compound (C1)), and 4.5 parts by mass of a photopolymerization initiator (D1) After uniformly stirring, it was diluted with ethyl acetate to prepare an active energy ray-curable composition (R3) having a nonvolatile content of 40% by mass. Using the obtained active energy ray-curable composition (R3), a test piece film was produced in the same manner as in Example 1, and then the appearance of the coating agent, the appearance of the cured coating film, the scratch resistance, the water contact angle, and the antifouling property were evaluated or measured. Light Slippery.

(Comparative Example 4)

In the same manner as in Example 1, except that the active energy ray-curable composition (R1) obtained in Comparative Example 1 was changed to an environment having an oxygen concentration of 5,000 ppm or less in the case where the test piece film was used. The appearance, the scratch resistance, the water contact angle, the antifouling property, and the smoothness of the cured coating film were evaluated or measured.

(Comparative Example 5)

The active energy ray-curable composition (R2) obtained in Comparative Example 2 was changed to an environment having an oxygen concentration of 5,000 ppm or less in the case where the test sheet film was prepared, and the same as in Example 1. The appearance, the scratch resistance, the water contact angle, the antifouling property, and the smoothness of the cured coating film were evaluated or measured.

The composition and evaluation results of the active energy ray-curable compositions used in the above Examples 1 to 9 and Comparative Examples 1 to 5 are shown in Table 1. In addition, the composition in Table 1 is described by the amount of nonvolatile components, and the urethane amides (A1) to (A6) are described as including the blending amount of PE4A or DPHA.

According to the evaluation results shown in Table 1, it was confirmed that the active energy ray-curable composition of the present invention, that is, the compositions of Examples 1 to 9 had no problem in appearance as a coating agent, and the appearance of the cured coating film was not problematic. Further, the surface of the cured coating film has excellent scratch resistance, antifouling property, and smoothness. In addition, when the oxygen concentration was 5,000 ppm or less in the production of the cured coating film, it was confirmed that the scratch resistance and the smoothness were improved.

On the other hand, in Comparative Example 1, an active energy ray-curable composition of a fluorine compound other than the fluorine compound (C) used in the present invention was used, and it was confirmed that the scratch resistance and the smoothness were insufficient. In addition, in Comparative Example 4 in which the oxygen concentration at the time of curing the active energy ray-curable composition was 5,000 ppm or less, the scratch resistance and the smoothness were also insufficient.

In Comparative Example 2, an acrylic resin having an acrylonitrile group was used instead of the active energy ray-curable composition of the urethane amide (A) used in the present invention, and it was confirmed that there was a problem in the appearance of the cured coating film. The scratch resistance and smoothness are not sufficient. In addition, in Comparative Example 5 in which the oxygen concentration at the time of curing the active energy ray-curable composition was 5,000 ppm or less, the appearance of the cured coating film was also confirmed to be problematic, and the scratch resistance and smoothness were confirmed. insufficient.

Comparative Example 3 used an acrylic urethane having 3 propylene groups instead of the hair. In the example of the active energy ray-curable composition of the urethane urethane (A) having four or more (meth) acrylonitrile groups used in the present invention, it was confirmed that the appearance of the coating agent and the appearance of the cured coating film were poor. The scratch resistance, antifouling property and smoothness are also significantly poor.

Claims (10)

An active energy ray-curable composition characterized by comprising: (meth)acrylic acid urethane (A) which is an aliphatic polyisocyanate (a1) and a (meth) acrylate having a hydroxyl group (a2) a compound having four or more (meth) acrylonitrile groups in one molecule, and a polyfunctional (meth) acrylate (B) having three or more (meth) propylene groups in one molecule. And a fluorine compound (C) having a cyclopolyoxyalkylene structure bonded to both ends of the poly(perfluoroalkyl ether) chain via a divalent linking group, and the above cyclic polyoxyalkylene oxide a structure in which a (meth)acryl fluorenyl group is bonded via a divalent linking group; the above polyfunctional (meth) acrylate (B) is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, or pentaerythritol. A mixture of a triacrylate and pentaerythritol tetraacrylate. The active energy ray-curable composition of claim 1, wherein the above (meth)acrylic acid urethane (A) system is used Alkyl diisocyanate used as the above aliphatic polyisocyanate (a1), and acrylamide obtained by using isophorone diisocyanate as the above aliphatic polyisocyanate (a1) The above polyfunctional (meth) acrylate (B) is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. A cured product obtained by irradiating an active energy ray-curable composition according to claim 1 or 2 with an active energy ray. A cured product obtained by irradiating ultraviolet rays to an active energy ray-curable composition according to claim 1 or 2 in a gas atmosphere having an oxygen concentration of 5,000 ppm or less. An article characterized by having a cured coating film of the active energy ray-curable composition of claim 1 or 2. A hard coat film comprising a hard coat layer on at least one side of a film substrate, the hard coat layer comprising a cured product of the active energy ray-curable composition of claim 1 or 2. The hard coat film of claim 6, wherein the hard coat layer has a thickness of 1 to 20 μm, and the base material has a thickness of 50 to 200 μm. A protective film characterized by having an adhesive layer on one side of a hard coat film as claimed in claim 6 or 7. The protective film of claim 8, wherein the thickness of the adhesive layer is 5 to 50 μm. A protective film according to claim 8 or 9, which is used for protecting an image display portion of a portable electronic terminal.